Ionothermal synthesis of aluminophosphate molecular sieve membranes through substrate surface conversion.

Applications of zeolite membranes in separation, chemical sensors, and catalytic membrane reactors have led to extensive studies on their fabrication. To date, mainly silicatebased zeolite membranes of the structure types MFI, DDR, LTA, and FAU have been synthesized on different substrates and evaluated for singleor multiple-gas permeation. Routes for the synthesis of zeolite membranes can be broadly classified into two categories: in situ and secondary growth synthesis, both of which are derived from the strategy of hydrothermal zeolite synthesis. However, the high autogenous pressure associated with hydrothermal procedures is inconvenient for preparation of zeolite membranes, especially for large-scale production, due to safety concerns and the risk of molecular sieve collapse. On the other hand, although aluminophosphate and silicoaluminophosphate membranes for gas separation have been prepared, there are few reports on the preparation of aluminophosphate molecular sieve membranes, which suggests that hydrothermal preparation of such membranes may be difficult. Ionothermal synthesis, which uses ionic liquids as reaction media instead of water or organic solvents, allowed highly efficient preparation of aluminophosphate molecular sieves under ambient pressure. Ionic liquids (ILs) are commonly defined as salts that consist of organic cations and inorganic anions with melting temperatures below 100 8C. ILs are well known as environmentally benign and designable solvents, which endow ionothermal synthesis with interesting features and many potential advantages over the hydrothermal method. As a result of the negligible vapor pressure of ILs, ionothermal synthesis can take place at ambient pressure, which eliminates safety concerns. The organic cation of the IL can act as a structure-directing agent (SDA), or play a cooperative structure-directing role together with introduced amines and quaternary ammonium compounds. AEL, AFI, CHA, LTA, and CLO types of aluminophosphate molecular sieves have been successfully synthesized by ionothermal methods. Ionothermal synthesis is a promising method for the preparation of aluminophosphate molecular sieve membranes under ambient pressure. Yan and co-workers prepared AlPO-11 and SAPO-11 films on aluminum alloys as anticorrosion coatings by in situ ionothermal synthesis. To the best of our knowledge, no permeable membrane has been previously prepared on a porous substrate by the ionothermal method. Here we report an ionothermal method for the synthesis of permeable aluminophosphate molecular sieve membranes on porous alumina disks by substrate-surface conversion. Molecular sieve membranes of types AEL, AFI, CHA, and LTA were prepared by placing homemade d-alumina substrates (2.0 mm thickness, 20 mm diameter, and 10 nm average pore size; see Supporting Information for details) in a solution of IL, phosphoric acid, hydrofluoric acid, and, if required, organic amines with no additional source of Al. Table 1 lists the initial solution composition, crystallization